Motor fuel



United States Patent 3,408,170- MOTOR FUEL Roy J. Betty, Chicago, 111., assignor to Armour and Company, Chicago, 111., a corporation of Delaware N0 Drawing. Filed Mar. 8, 1967, Ser. No. 621,438 11 Claims. (Cl. 44-74) ABSTRACT OF THE DISCLGSURE An improved hydrocarbon fuel composition containing a minor proportion, sufficient to improve the deicer and detergent characteristics thereof, of an aryl substituted alkyldiamine.

Background of the invention My invention releates to an improved hydrocarbon fuel composition containing a novel additive agent which functions as a combined deicer-detergent.

Stalling and rough idling is a frequent problem in sparkignition internal combustion engines, particularly those incorporating high-compression engine design improvements and thereby having stringent fuel requirements.

A primary cause of such poor engine performance is the accumulation of gum and dirt deposits in the fuel induction system, particularly in the intake manifolds, on the intake valves and in the carburetor. The trouble-causing deposits result primarily from contaminants in the carburetor intake air such as engine blowby, smoke, exhaust and dust. Deposit build-up in the throttle-body section of the carburetor is particularly onerous, as here the deposits directly affect the air-to-fuel ratio presented to the carburetor and especially disrupt the idling qualities of the engine.

During cold, humid weather, a stalling problem is encountered during the engine warm-up. Stalling under these conditions is generally recognized to be due to a factor other than gum and dirt deposits. Gasoline fuel, having the desired volatile characteristics for cold weather driving, evaporates in the carburetor causing moisture present in the air and in the gasoline to condense and freeze. As ice particles build up in the throttle-body section of the carburetor, the air passageway between the throttle and the carburetor body becomes blocked and the engine stalls.

Many gasoline additives have been developed for the separate purposes of deicing or detergency. Additives which work well for either one of thesepurposes generally are not effective for the other.

Deicer additives form a film on the carburetor surfaces. This film renders the surfaces oil-Wetted with gasoline and prevents moistures adherence. Some deicer additives, such as isopropanol, lower the freezing point of water so that ice particles never form. Even though ice particles may form, the film prevents their adherence to carburetor surfaces, thereby preventing ice blockage of the throttlebody passageway.

Detergent additives function to reduce the existing gum and dirt particle deposits and to prevent the formation of additional deposits in the fuel induction system of sparkignition internal combustion engines.

Summary of the invention 3,4&17U Patented Oct. 29, 1968 "ice boiling within the gasoline boiling range, and a minor proportion of an aryl subsituted alkyldiamine possesses excellent properties as a combination carburetor deicer-carburetor detergent additive motor fuel.

Therefore it is an object and advantage of my invention to provide an improved hydrocarbon fuel composition for more efficient operation of spark-ignition internal combustion engines. lit is, more particularly, an object of my invention to provide an improved hydrocarbon fuel composition eifective for inhibiting the formation of gum and dirt deposits and of ice particle build-up in the induction system of spark-ignition internal combustion engines. A further object is to provide an improved hydrocarbon fuel composition effective for the removal of pre-existing gum and dirt deposits and the inhibition of ice particle buildup in the fuel induction system of spark-ignition internal combustion engines. Other specific objects and advantages of my invention will appear as the specification proceeds.

Detailed description of the invention A specific embodiment of the gasoline and fuel com position of my invention may be exemplified by the composition comprising a major proportion of a hydrocarbon base fuel, boiling within the gasoline boiling range, and a minor proportion of an aryl substituted alkyldiamine having the formula:

wherein Ar is an aryl radical selected from the group consisting of phenyl, naphthyl and phenyl substituted with from 1 to 2 groups selected from methyl, hydroxy and methoxy, x and y each are integers from 0 to 19 and the total of x and y is an integer from 8 to 19, and z is an integer from 2 to 6. In a preferred sub-class within the above formula Ar is phenyl, z is 3, and the other variables have the designations previously assigned. In another preferred sub-class within the above formula Ar is phenyl, z is 3, x and y are integers from 0 to 15, and the total of x and y is 15. Relatively small quantities of the aryl substituted alkyldiamine are suflicient to obtain the combined deicer-detergent effect of the present invention. Excellent results have been obtained when the additive constitutes about 20 to 500 parts per million parts of the fuel. We prefer to employ from about 50 to ppm. of the gasoline additive to achieve the objectives of this invention. It will be understood that concentrations below the ranges just set out will provide some degree of effectiveness. Likewise, higher concentrations than those referred to will provide satisfactory results, although there are practical considerations which limit the desirability of much greater amounts of additive.

The additives of this invention may be prepared in accordance with conventional procedures by first, arylation of the corresponding chain length unsaturated fatty acid, and then conversion of the arylated fatty acid to the diamine. For example, phenylation of stearic acid (or other long chain fattty acid) may be accomplished using HF as a catalyst, as described in Patent 2,275,312, or using an activated clay, as described in Patent 3,074,983. The phenylstearic acid can then be converted to the corresponding nitrile, the nitrile converted to the primary amine, and the primary amine converted to the diamine, by conventional hydrogenation procedures, to result in, for example, N-(9,l0-phenylstearyl)-l,3,-trimethylene diamine.

Referring to the above formula, the carbon to which the aryl constituent is attached varies with the respective values of x and y. With unsaturated alkylene chains, such as oleyl, the double bond migrates up and down the chain (isomerization by hydrogen ion transfer) resulting in a mixture of isomeric products. For example, in phenylation of oleyl there is a tendency for the C -C and the C phenyl isomers to predominate, but smaller mole percentages of other isomers are also produced, such as the C -C C and C isomers. Although the relative proportions of the various isomers may vary depending on the arylation process (see J. Org. Chem. 30, 885-888, 1965), the total of x and y will remain constant for the particular unsaturated chain; that is 15 for oleyl, 8 for undecyl, 19 for behenyl, etc. By phenylation, oleic acid is converted to phenyl substituted stearic acid. Similarly, palmitoleic, erucic, and IO-undecenoic acids can be converted to the corresponding aryl substituted carboxylic acids.

The preferred aryl constituent for the additive of my invention is phenyl. Other desirable aryl groups include hydroxyphenyl, tolyl, anisyl, xylyl and naphthyl. More generally, the phenyl nucleus may be substituted with 1 or 2 groups such as methyl, hydroxy and methoxy.

The additives of my invention also contain an alkylene group between the nitrogen atoms. While this group may contain from 2 to 6 carbons, 3 carbons (trimethylene) are preferred; and z is therefore an integer from 2 to 6 and preferably 3.

Non-limiting examples of eifective phenyl substituted diamines within the defined class include N-phenyloctadecyltrimethylene diamine and isomeric mixture of N- phenylsterayltrimethylene diamine, N-phenylundecyltrimethylene diamine, N-phenyldocosyltrimethylene diamine.

The additives of this invention may be used in association with other gasoline additives and with solvents.

The following specific examples illustrate the unique deicer-detergent characteristics of hydrocarbon fuel, boiling within the gasoline boiling range, having incorporated therein particular aryl substituted diamines of this invention.

EXAMPLE I A 1962 Chevy II, 6 cylinder engine, was employed to evaluate carburetor detergency. Each test comprised running the engine with 3 liters of fuel at an idle speed of 600 r.p.m. under a no load condition. The engine was run until the fuel was used up (about 1 /2 hours). The carburetor was freshly cleaned prior to each test; and during the test the blowby gas was brought back intthe carburetor to accelerate deposit build-up. Following each test, the carburetor was removed, dismantled and inspected visually as to the percentage of the area under the throttleplate and throttle-plate area free from deposits. Table I sets out exemplary comparative results of tests conducted according to the above procedure. Each test utilized the fuel composition noted.

TABLE I.MOTOR FUEL DETERGENCY TEST Additive Rating (percent Fuel (p.p.m.) clean area under throttle plate) Base 1 0 20-30 Base+Ethyl MPA 2 50 65 Base+N-phenylstearyl trimethylene {25 90 diamine. 50 100 l The base fuel employed was a commercial leaded gasoline representative of nationally-available commercial gasolines (without additives).

Ethyl multi-purpose additivea mixture of two amides produced by the reaction of oleic acid and B-hydroxyethyl ethylene diamine, manufactured by Ethyl Corporation. I

EXAMPLE II A standard deicer test apparatus was employed to evaluate carburetor deicing. The test conditions of the deicer test are 42 F. and 85% relative humidity. Each test is run for 6 minutes. The results of each test are obtained by readings taken from a monorneter every 30 seconds. At the conclusion of each 30 second interval, temperature, vacuum and gasoline consumption are recorded. The chemical additive having the lowest vacuum reading at the end of 6 minutes exhibits the least amount of; ice adherence or formation on the throttle-plate and throttle-plate area of the carburetor, and is rated the best potential deicer. All tests recorded are started with a manifold vacuum of 4 inches. Table 11 presents exemplary results of tests conducted according to the above procedure. Each test utilized the fuel composition noted.

TABLE II.MOTOR FUEL DEIGER TEST 1 The base fuel employed was a commercial unleaded gasoline representative o f commercially-available, full boiling range winter grade base gasoline with no additives. It had a Reid vapor pressure of 13.5 p.s.i. and an ASTM 50% boiling point of 181 F.

3 Average.

The foregoing data show the outstanding combination deicer-detergent properties of the aryl substituted alkyldiamines of this invention.

The foregoing specification has set out specific compositions and quantities in considerable detail for the purpose of illustrating some embodiments of this invention. It is clear that the compositions and quantities may be varied widely by those skilled in the art without departing from the spirit and scope of this invention.

I claim:

1. An improved gasoline composition comprising a major proportion of a hydrocarbon base fuel, boiling within the gasoline boiling range, and a minor proportion sufficient to improve the deicer and detergent characteristics thereof, of an aryl substituted alkyldiamine having the formula:

wherein Ar is an aryl radical selected from the group consisting of phenyl, naphthyl and phenyl substituted with from 1 to 2 groups selected from methyl, hydroxy and methoxy, x and each are integers from 0 to 19 and the total of x and y is from 8 to 19, and z is an integer from 2 to 6.

2. The composition of claim 1 in which Ar is phenyl and z is 3.

3. The composition of claim 1 in which Ar is phenyl, z is 3, and x and y are integers from 0 to 15, and the total of x and y is 15.

4. The composition of claim 1 in which said minor proportion is from 20 to 500 p.p.m.

5. The composition of claim 4 in which said minor proportion is from about 50 to p.p.m.

6. An improved gasoline composition comprising a major proportion of a hydrocarbon base fuel, boiling within the gasoline boiling range, and a minor proportion suificient to improve the deicer and detergent characteristics thereof, of aryl substituted alkyldiamines having the formula:

wherein Ar is an aryl radical selected from the group consisting of phenyl, naphthyl and phenyl substituted with from 1 to 2 groups selected from methyl, hydroxy and methoxy, x and y each are integers from 0 to 19 and the total of x and y is from 8 to 19, and z is an integer from 2 to 6, said alkyldiamine being in the form of an isomeric mixture.

, 7. The composition of claim 6 in which said mixture is of N-phenylstearyltrimethylene diamine.

8. The composition of claim 6 in which said mixture is of N-phenylundecyltrimethylene diamine.

9. The composition of claim 6 in which said mixture References Cited is of N-phenyldocbsyitrimeihylcne dial-nine- P 10. An improved gasoline composition comprlsmg a major porportion of a hydrocarbon base fuel, boiling with- 25 12,29 7 6/1950 Blsweu et 4472 XR in the gasoline boiling range, and a minor proportion suf- 5 2,706,677 4/1955 Duncan et a1 XR ficient to improve the deicer and detergent characteristics 2,891,850 6/1959 Cosgrove et 44"72 thereof, of N-(9-l0-phenylsteary1)-1,3-trimethylene di- 3,050,043 8/1962 Barusch 44-72 XR amine.

11. The composition of claim 10 in which said minor DANIEL WYMAN Primary Examiner proportion is from 20 to 500 p.p.m. 10 W. J. SHINE, Assistant Examiner. 

